Chromiferous azo dyestuffs containing an 8-hydroxyquinoline radical



3,158,512 Patented Feb. 2, 1965 t d m Pat we i t 3,163,512 ClHMIFEROU A226) DYESTUIFF CQNTAFNHJG AN 8-HYDRUXYQUENQHNE RADECAL Arthur Buehler, Rheinielden, Switzerland, and Gerhard Back, Loerrach, Germany, assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Filed Apr. it), H61, Ser. No. 101,667 Claims priority, application witzerland, Apr. 11, 1960, 4,078/60; Mar. 16, 1961, 3,179/61 8 Claims. (Cl. 260-146) The present invention is based on the observation that new, valuable chromiferous azo dyestuffs are obtained by reacting in the molecular ratio of about 1:1 an S-hydroxyquinoline which may contain a sulfonic acid group with a complex chromium compound of an ortho:ortho-dihydroxy-ortho-carboxy ortho' hydroxy-, ortho carboxyortho'-amonoor ortho-hydroxy-ortho-aminoazoor ammethine-dyestutl containing one or more sulfonic acid or carboxylic acid groups and per molecule of dyestuft one atom of chromium bound in complex union.

As S-hydroxyquinolines there are suitable compounds that are free from, or contain, sulfonic acid groups, for example 6:8-dihydroxyquinoline, S-chloro-S-hydroxyquinoline, 8-hydroxyquinoline-7-su1tonic acid and above all S-hydroxy quiuoline itself.

Themonoazo dyestuils containing one or more sultonic acid groups to be used in the present process in the form of their lzl-chromium complexes can be prepared in known manner by coupling an ortho-hydroxydiazo or ortho-carboxy-diazo compound, primarily such as belong to the benzene or naphthalene series, with coupling components capable of coupling in ortho-position to an amino or hydroxyl group. The lzl-chromium complex compounds to be used may contain a Wide variety of nonionic substituents such as chlorine atoms, or nitro, alkyl, alkoxy, alkylsulfoxide, alkylsulfone, sulfonamide or acylamino groups. Particularly valuable results are achieved with the 1:1-chromium complex compounds of ortho-hydroxy-ortho-amino-azo dyestuffs of the benzeneazonaph thalene series containing one or more sulfonic acid groups whose benzene nucleus contains a nitro group, furthermore 1: l-chromium complex compounds of monoazo dyestuffs containing as diazo component a 4-chloro-2-aminophenol-6-sulfonic acid or a 2-hydroxy-l-arnino-naphthalene-4-sulfonic acid.

' For the manufacture of monoazo dyestuffs whose 1:1- chromium complex compounds are used as starting materials the diazo compounds of the undermentioned amines-more especially such as contain a nitro groupcan be coupled, for example, with the following coupling components capable of coupling in a vicinal position to the amino or hydroxyl group respectively:

Z-aminonaphthalene, 2-amino-6-alkoxynaphthalene, 2-aminonaphthalene-fi-sulfonic acid morpholide, 2-aminonaphthalene-G-sulfonic acid-N-methyl-,

-ethy1-, isopropy1-, -fi-hydroxyethylor methoxypropylamide, 2-aminonaphthalene-G-sulfonic acid anilide, 2-aminonaphthalene-G-sulfonic acid-N-methylanilide, l-aminonaphthalene-3-, -4- or -5-sulfonamides, l-aminonaphthalene-S-methylor -ethylsulfone, 2-aminonaphthalene-6 sulfonic acid phenyl ester, 5:S-dichloro-l-aminonaphthalene, r

. 2-phenylaminonaphthalene,

2-pheny1amino-naphthalenesulfonamides, 2-(3'-chlorophenylamino)-naphthalenesulfonamides, 2- sulfonamido -phenylaminonaptl1 alenes, 2-hydroxynaphthalene,

l-hydroxy-S S-dichloronaphthalene, l-hydroxy-7-acylaminonaphthalenes,

furthermore naphtliylamines containing sulfonic acid groups or carboxylic acid groups such as as well as compounds capable of coupling in vicinal position to an enolized keto group such as 5-pyrazolones, for example:

1-phenyl-3-methy1-5-pyrazolone, 1phenyl-3-methyl-5-pyrazolone-3'- or -4-sulfonic acid, 1- 2-methy1-6'-chlorophenyl) -3-methyl-5pyrazo1one, 1- (2'5 -dich1orophenyl) -3-methyl-5-pyrazolone-4'- sulfonic acid, or acetoacetic acid amides, more especially acetoacetic acid arylides. As examples of suitable diazo compounds there may be mentioned those of the following amines:

3 :4: 6-trichloro-2-aminol-hydroxybenzene,

4 6-dichloro-2-amino-l-hydroxybenzene,

4- or 5-chloroa2-amino-l-hydroxybenzene,

2-amino-l-hydroxybenzenelor -5-sulfonamides and -sulfones, t

Z-amino-1-hydroxybenzene-4- or 5-sulfonic acid,

4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid,

and more especially compounds containing nitro groups such as 1 4-= or S-nitro-Z-amino-l-hydroxybenzene, 4.-chlo-ro-5- or -6-nitro-2-amino-l-hydroxybenzene, 4-nitro-6-chloroZ-amino-1-hydroxybenzene, 6nitro-4-methyl-2-amino-l-hydroxybenzene, 4-nitro-6-acetylamino-2-amino-l-hydroxybenzene, 6-nitro-4-acetylamino-2-amino-l-hydroxybenzene,

, 4:6-dinitro-2-amino-l-hydroxybenzene,

fone, 6-nitro-2-hydroxy-1-aminonaphthalene-4-sulfonic acid, 4-nitro-2-amino-l-hydroxybenzene-5- or -6-sulfonic acid, 6-nitro-2-amino-1-hydroxybenzene-4-sulfonic acid, 2-hydroxy-1-aminonaphthalene 4-sulfonic acid,

4-nitro-2-amino-l-hydroxybenzene-S- or -6-methylsul- 2-hydroxy-6-nitro-1-aminohaphthalene-4-sulfonic acid, furthermore anthranilic acid.

. The components to be coupled must always be selected.

so that the monoazo dyestufi contains at least one sulfonic acid group. The azomethine dyestulls which are likewise suitable as starting materials for the present process can be manufactured by known methods.

In other respects, the lzl-complexes used as starting materials in the present process may be manufactured by any desired known method, for example by reacting a metallizable monoazo dyestulf or azomethine dyestufi that is free from complex-forming metal in an organic medium, (for example in a water miscible medium such as pyridine, formamide, dioxane or the like) or'in an aqueous acid medium with an excess of a salt of trivalent chromium such as chromium acetate, chromium formate, chromium chloride, chromium sulfate or chromium fluoride at the boil or preferably at a temperature exceeding C.

The reaction, according to the present invention of the 3 lzl-chromium complex with the 8-hydroxyquinoline is caried out in an organic medium or in an aqueous medium of weakly acid, neutral to alkaline reaction, under atmospheric or superatmospheric pressure, at room temperature or an elevated temperature, for example at a temperature ranging from 50 to 120 C. In general it is advisable to use for the reaction as far as possible equivalent proportions of the metalliferous lzl-complex and of the 8- hydroxy-quinoline.

As an alternative to preparing first the lzl-chromium complex compounds theproducts obtained by the present process may be made by chroming the metallizable monoazo dyestufi' or azomethine dyestutf in the presence of a hydroxy-quinoline compound.

According to another variant of the present process the chromium complex is first made from one atomic proportion of chromium, one molecular proportion of one of the aforementioned monoaz'o dyestuffs and one molecular proportion of an organic compound capable of forming chromium complexes but which is not a dyestuif whereupon in said chromium complex the complex-forming organic compound is replaced by an 8-hydroxyquinoline. As such compounds that are capable of forming complexes but posses no dyestuff character there may be used, for example, aromatic compounds containing hydroxyl groups and/ or carboxyl or sulfonic acid groups such as 1:2-dihydroxybenzene, orthoor peri-dihydroxynaphthalenes, ortho-hydroxynaphthoic acids, phthalic acid and derivatives thereof and more especially salicylic acid, furthermore pyridinesulfonic or carboxylic acids, oxalic, tartaric, citric or malic acid, polyglycols or ethanolamines.

The chromiferous monoazo and azomethine dyestuffs obtained by the present process or one of its variants are new; they are surprisingly stable and are suitable for dyeing or printing a wide variety of materials, above all for dyeing animal materials such as silk, leather and more especially wool, and are also suitable for dyeing or printing synthetic fibers of superpolyamides or superpolyurethanes. They can be used for dyeing nitrogenous fibers such as wool, for example from a bath of acetic acid to neutral reaction, if desired with addition of the assistants conventionally used in dyeing, for example with addition of compounds containing at least one basic nitrogen atom to which is bound at least one residue containing a polyglycol ether chain, the molecule containing at least three Jae-- I groups (preferably CH CH -O-- groups) and at least four carbon atoms not belonging to such a group, for example with addition of a nitrogen compound of the formula CHT"CH2 O) 9-H where R represents a preferably unbranched aliphatic hydrocarbon radical containing at least 12, preferably 16 to 22, carbon atoms; in and n=1 or 2; p, q and I are whole numbers, the sum p+q+ (m-l)(rl) being at least 3 and preferably from 6 to 20.

Furthermore, nitrogenous fibers, more especially wool, can =bedyed in an advantageous manner with dyestuffs obtained by the present process by applying to the fiber, advantageously continuously, for example on a padder, an aqueou preparation containing a wool dyestuif and an assistant capable of forming with water and if desired with additives a system which consists of two liquid phases and displays a mixture gap, the ratio of water (if desired containing additives) to the assistant being within or in the proximity of the mixture gap, the mixture gap appearing already at a relatively low content of assistant, and the phase richer in assistant making up a substantial share of the mixture within a wide range of the mixture gap, the fiber material impregnated with the aqueous preparation then being subjected to a heat treatment.

A group of compounds that satisfies the abovementioned conditions and is preferably used in performing the present process includes hydrophilic, more especially surfactive substances forming colloidal solutions and capable of coacervation.

As examples of assistants that satisfy the above-mentioned requirements and are capable of coacervation, and are therefore particularly suitable for the process described above, there may be mentioned the reaction products of higher fatty acids with hydroxyalkylamines, and if desired with ethylene oxide. It is possible for example, to manufacture such products without using ethylene oxide from higher fatty acids, preferably such as contain about 12 carbon atoms, and hydroxyalkylamines such as triethanolamine or preferably diethanolamine, the reaction taking a course such that the molecular ratio of hydroxyalkylamine to fatty acid is greater than unity, being, for example, about 2:1.

The fiber impregnated with the two-phase system is then subjected to thermofixation, generally performed with steam or in exceptional cases with dry heat.

The heat-treated material must then be cleaned to remove any excess dyestuff, thickener and residual assistant. As a rule this cleaning takes the form of a treatment in a heated bath containing a surfactive detergent, if desired in the presence of ammonia or of an acid.

As a rule, dyeings and prints obtained with the new dyestuffs are distinguished by their levelness, the purity of their tints, by good fastness to light and good fastness to abrasion; in general their appearance in artificial light hardly changes at all and some of them have very pleasing and valuable shadm.

Unless otherwise indicated, parts and percentages in the following examples, which illustrate the invention, are by weight. The relationship between parts by weight and parts by volume is the same as that between the gram and cm.

EXAMPLE 1 37.4 parts of the lzl-chromiurn complex of the dyestuff from diazotized 1-hydroxy-2-amino-5-nitrobenzene and Z-naphthylamine-6-sulfonic acid, with the addition of 50 parts of N-sodium hydroxide solution in 500 parts of water heated at about 50 C., are stirred until a clear solution forms. A solution cleared by filtration and heated to about 50 C., of 22.7 parts of 8-hydroxyquinoline-7-sulfonic acid in 200 parts of water and 50 parts of N-sodium hydroxide solution are then added and the reaction mixture is heated to to C. while being stirred. During the stirring the solution changes color from greenish blue to pure green. In completion of the reaction the whole is filtered, if desired with the aid of a filter assistant such as Celit, carbon or the like. The dyestufi formed is salted out with sodium chloride, filtered oif and dried in vacuum at 95 C. The resulting dyestuif is soluble in water with pure green coloration and in concentrated sulfuric acid with red-violet coloration and yields by the process described above on wool pure, bluish green dyeings.

A similar dyestufi is obtained when the lzl-chromium complex dyestuff is reacted with 14.8 parts of 8-hydroxyquinoline instead of with 8-hydroxyquinoline-7-sulfonic acid.

EXAMPLE 2 32.0 parts of the monoazo dyestuif from diazotized complex formed is isolated by pouring the reaction mixture into 3000 par-ts of a solution of sodium chloride of 20% strength heated to about 60 C. The whole is stirred for some time and then filtered and the filter cake is Washed with sodium chloride solution of 20% strength and then dried in vacuum at 95 C. The properties of the resulting dyestulf correspond to those of the dyestufit' mentioned at the end of Example 1.

The reaction of the metalfree components may alternatively be carried out in an aqueous suspension of Weakly 6 t acid to alkaline reaction at an elevated temperature and under superatmospher-ic pressure.

EXAMPLES 3 TO 39 When the lzl-chromium complexes of the monoazo dyestuifs listed in column I of the following table are reacted with the colorless complex-formers shown in column II by the process described in Example 1, there are obtained further dyestuffs of similar properties which produce on wool the shades listed in column III.

II III on 1 :3 3.-.- o,N- N=N Green.

No, S0 11 no K OH NH;

4..-- H0 8 N=N Olive green.

Ho s- 1 I H 3TH NH:

5...- N= Green. 2

on NB,

6---. N=N D0.

o,N- 0 H (])IEI NH;

11.-- Olive.

III

Gren.

BIue-green.

Green.

Yellowlsh green.

Green.

Green-blue.

Orange.

Gray.

Black.

SOaH

0H 21m g I n m OH OH 32... 01- N=N Grey.

No; 5031-1 H OH H 33... =CH Yellow.

OH HgN 34 01; N=N- [n Olive.

N son (in 0 H Hz 3 1H 35..- N=N- Do.

No, 0111 H OH. mN c1 36... 7 N=N Green.

0 gN- S O H H 0 s 0 H HIN I 37.-- Ohms Do.

I 0 3H H 011 EN as.-- Hms- N=N (I) Do:

N 1 (BE CODE 11, 39.. N= -8 Red-violet.

Directions for dyeing knitting wool 60 C. in a dyebath consisting of 3000 parts of water,

65 parts of acetic acid of 40% strength, parts of sogg fi g gg gg wzi $3332 dium sulfate, 2 parts of the ethylene oxide adduct preans mm v sulfate ar id 1 part if the dyestufi d escribed at the end par-ed descnbed below and 1 part. of t dyest E descnbed m Example 1. The bath 1s ransedwithin /2 of Example 1. In the course of /2 hour the bath is hour to the boll and the fabric is dyed for another hour 0 ralsed to the boil and the wool is dyed for another hour 7 at 1 e bo-l, 1 e Se] 1 1 ied. level ee y g at the boil, then rinsed and dried. A level green dyeing is obtained. 1s obtained.

Directions for dyeing woolen fabrics 1 Prep the ethylene Oxide adduct 100 parts of woollen fabric are immersed at 5 0 to A mixture of parts of commercial oleylarnine and 1 part of finely distributed sodium is heated to 140 C., whereupon ethylene oxide is introduced at 135 to 140 C. When the ethylene oxide is being consumed rapidly, the reaction temperature is lowered to 120 to 125 C. and the introduction of ethylene oxide is con tinued until 113 parts thereof have been taken up. The resulting reaction product gives a substantially clear solution in water.

What is claimed is:

1. A complex chromium compound containing one atom of chromium in complex union with substantially one molecule of a member selected from the group consisting of S-hydroxyquinoline and S-hydroxyquinoline- 7-sulfonic acid and with substantially one molecule of the monoazo dyestutf sulfonic acid corresponding to the formula (3H X U 8 Y W in which D represents the radical of naphthalene bound to the azo linkage in vicinal position to the hydroxyl group and A is the radical of pyrazolone bound to the azo linkage in 4-position.

3. The complex chromium compound containing one atom of chromium bound in complex union with substantially one molecule of 8-hydroxyquinoline and With substantially one molecule of the mouoazo dyestufi of the formula:

OH HO 4. The complex chromium compound containing one atom of chromium bound in complex union with substantially one molecule of 8-hydroxyquinoline and with sub- 14 stantially one molecule of the monoazo dyestuft of the formula OH NH:

5. The complex chromium compound containing one atom of chromium bound in complex union with substantially one molecule of 8-hydroxyquinoline and with substantially one molecule of the monoazo dyestutf of the formula OH NH:

6. The complex chromium compound containing one atom of chromium bound in complex union with substantially one molecule of 8-hydroxyquino1ine and with substantially one molecule of the monoazo dyestufl? ofthe 7. The complex chromium compound containing one atom of chromium bound in complex union with substantially one molecule of 8-hydroxyquinoline and with substantially one molecule of the monoazo dyestufi of the formula J31 Ha 8. The complex chromium compound containing one atom of chromium bound in complex union with substantially one molecule of 8-hydroxyquinoline and with substantially one molecule of the monoazo dyestufi of the formula HO S- References Cited in the file of this patent UNITED STATES PATENTS Pfitzner et a1. Aug. 3, 1954 Pfitzner et al. May 10, 1955 Ackermann et al. Feb. 18, 1958 

1. A COMPLEX CHROMIUM COMPOUND CONTAINING ONE ATOM OF CHROMIUM IN COMPLEX UNION WITH SUBSTANTIALLY ONE MOLECULE OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF 8-HYDROXYQUINOLINE AND 8-HYDROXYQUINOLINE7-SULFONIC ACID AND WITH SUBSTANTIALLY ONE MOLECULE OF THE MONOAZO DYESTUFF SULFONIC ACID CORRESPONDING TO THE FORMULA
 2. A COMPLEX CHROMIUM COMPOUND CONTAINAING ONE ATOM OF CHROMIUM IN COMPLEX UNION WITH SUBSTANTIALLY ONE MOLECULE OF THE 8-HYDROXYQUINOLINE AND WITH SUBSTANTIALLY ONE MOLECULE OF THE MONOAZO DYESTUFF OF THE FORMULA
 3. THE COMPLEX CHROMIUM COMPOUND CONTAINING ONE ATOM OF CHROMIUM BOUND IN COMPLEX UNION WITH SUBSTANTIALLY ONE MOLECULE OF 8-HYDROXYQUINOLINE AND WITH SUBSTANTIALLY ONE MOLECULE OF THE MONOAZO DYESTUFF OF THE FORMULA: 